CN107615546A - Redox flow batteries - Google Patents

Redox flow batteries Download PDF

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Publication number
CN107615546A
CN107615546A CN201680030436.2A CN201680030436A CN107615546A CN 107615546 A CN107615546 A CN 107615546A CN 201680030436 A CN201680030436 A CN 201680030436A CN 107615546 A CN107615546 A CN 107615546A
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CN
China
Prior art keywords
electrode
passage
bipolar plates
electrolyte
recess
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Pending
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CN201680030436.2A
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Chinese (zh)
Inventor
花房庆
伊藤贤
伊藤贤一
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Publication of CN107615546A publication Critical patent/CN107615546A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/666—Composites in the form of mixed materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04276—Arrangements for managing the electrolyte stream, e.g. heat exchange
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
    • H01M2250/10—Fuel cells in stationary systems, e.g. emergency power source in plant
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02B90/10—Applications of fuel cells in buildings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a kind of redox flow batteries, the redox flow batteries include：Electrode, electrolyte is supplied to the electrode；Barrier film, the barrier film are configured in a manner of the first surface in face of the electrode；And bipolar plates, the bipolar plates are configured in a manner of the second surface in face of the electrode.The bipolar plates have passage on its surface in face of the electrode, the electrolyte flows through the passage, and the electrode has multiple recesses in its region in face of the passage, the recess guides the electrolyte in the passage from the side of the laterally closer barrier film close to the bipolar plates.

Description

Redox flow batteries
Technical field
The present invention relates to redox flow batteries.
Background technology
In recent years, because electricity shortage turns into serious problems, it is therefore desirable to be immediately introduced such as wind-force in the world Generating or the natural energy resources of solar energy power generating, and need stable power system (such as keep frequency or voltage).Closed One of countermeasure technology of note is installation large-capacity battery so that exporting change tranquilization, storage dump power, balanced load etc. Deng.
A kind of large-capacity battery is redox flow batteries (hereinafter, commonly referred to as RF battery).RF batteries have Such as following characteristics：(1) it is easy to capacity increasing to megawatt (MW) level；(2) long-life；(3) it is capable of filling for accurate measurements battery Electricity condition (SOC)；(4) cell output and the high design freedom of battery capacity can be independently engineered, it is contemplated that be to use In the suitable battery of stable power system.
RF batteries generally have the battery unit as main member, and the battery unit includes being supplied anode electrolyte Positive pole, be supplied the negative pole of electrolyte liquid and the barrier film being arranged between positive pole and negative pole.It will be called including for battery pile The heap of multiple battery units is used for Large Copacity purposes.In many cases, bipolar plates are set between adjacent battery unit.Just Pole and negative pole are each using the porous body (patent document 1, patent document 2) of such as carbon felt, and bipolar plates use such as plasticity The board member (patent document 2) of carbon.
RF batteries are generally used by constructing RF battery systems, and the RF battery systems are included in a looping fashion to RF electricity The cycling mechanism of electrolyte is supplied in pond.Cycling mechanism includes：Store the electrolyte of each electrode groove, by the groove of each electrode with Pump of the pipeline and configuration of RF batteries connection on pipeline.Patent document 1, which describes two electrodes, all has specific groove And therefore energy loss (pressure loss) hardly increases as caused by pump.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2002-246035 publications
Patent document 2：Japanese Unexamined Patent Publication 2002-367659 publications
The content of the invention
Technical problem
For redox flow batteries, even if when working current density increase, it is also desirable to reduce the change of cell voltage Change amount.
For example, when discharge current density increase, by increasing capacitance it is possible to increase the power output of per unit area, therefore be expected to reduce electricity Chi Dui cost.However, when discharge current density increase, cell voltage declines.Therefore, it is desirable to reduce the decline of cell voltage And reduce the cell voltage amount of changing with time.
Described in test example 1 as be described hereinafter, find using plate electrode and the RF batteries of the bipolar plates without groove even in work Also small cell voltage variable quantity is produced when making current density increase.However, if the area for being intended to increase electrode is held with increasing Amount, then use the plate electrode of no groove and the bipolar plates without groove cause due to the flow resistance of electrolyte and it is caused big The pressure loss.If electrode has specific groove as described in patent document 1, the pressure loss can be reduced.However, work as work When current density increases, even if this construction is still insufficient as reducing the countermeasure of the variable quantity of cell voltage.
In these cases, it is an object of the present invention to provide can also reduce when working current density increase The redox flow batteries of the variable quantity of cell voltage.
Technical scheme
The redox flow batteries of one aspect of the invention include：Electrode, electrolyte is supplied to the electrode；Barrier film, The barrier film is configured in a manner of the first surface in face of the electrode；And bipolar plates, the bipolar plates are with face of the electricity The mode of the second surface of pole configures.
The bipolar plates have passage on its surface in face of the electrode, and the electrolyte flows through the passage.
The electrode has multiple recesses in its region in face of the passage, and the recess is by the electricity in the passage Liquid is solved from the guiding of the side of the laterally closer barrier film close to bipolar plates.
The beneficial effect of invention
Above-mentioned redox flow batteries still are able to reduce the change of cell voltage when working current density increase Amount.
Brief description of the drawings
[Fig. 1] Fig. 1 is the bipolar plates schematically shown included in the redox flow batteries of embodiment 1, electrode Illustrate figure with the cross section of the arrangement states of barrier film.
[Fig. 2] Fig. 2 is included in the exploded perspective of the bipolar plates and electrode in the redox flow batteries of embodiment 1 Figure.
[Fig. 3] Fig. 3 be from electrode side be included in embodiment 1 redox flow batteries in bipolar plates and The plan view during arrangement states of electrode.
[Fig. 4] Fig. 4 is the redox flow battery system for showing the redox flow batteries comprising embodiment 1 Essential structure and the explanation figure of basic functional principle.
[Fig. 5] Fig. 5 is show example battery heap included in the redox flow batteries of embodiment 1 schematic Structural map.
[Fig. 6] Fig. 6 is the pass between the current density for the polarization characteristic experiment for representing to carry out in test example 1 and cell voltage The curve map of system.
[Fig. 7] Fig. 7 be the current density for the polarization characteristic experiment for representing to carry out in test example 1 with initial cell voltage and surely Determine the curve map of the relation between the voltage difference of cell voltage.
Embodiment
[explanation of embodiment of the present invention]
In working current density increase in order to reduce the variable quantity of cell voltage, redox flow batteries can be reduced Internal resistance.The inventors discovered that to reduce the variable quantity of cell voltage, the expansion being included in internal resistance is especially reduced Scattered resistance is effective, and the internal resistance is conductor resistance, reaction resistance and diffusion resistance sum, and by with spy The mode of setting shape designs bipolar plates and electrode, can substantially ensure that cell reaction field and reduce diffusion resistance simultaneously.The present invention It is to be found to be basis with above-mentioned.The content of embodiment of the present invention is illustrated first in the form of outlining.
(1) redox flow batteries (RF batteries) of embodiment include：Electrode, electrolyte is supplied to the electrode； Barrier film, the barrier film are configured in a manner of the first surface in face of the electrode；And bipolar plates, the bipolar plates are with face of institute The mode for stating the second surface of electrode configures.
The bipolar plates have passage on its surface in face of electrode, and the electrolyte flows through the passage.
The electrode has multiple recesses in its region in face of passage, the recess by the electrolyte in passage from by The side guiding of one laterally closer barrier film of nearly bipolar plates.
The recess can preferably include at least one of following：Through hole, the through hole is in electrode in face of described The surfaces (hereinafter sometimes called bipolar plates side surface) of bipolar plates and electrode in face of the surface of the barrier film (sometimes below Referred to as barrier film side surface) two surfaces at opening and extend from the bipolar plates side surface to the barrier film side surface；Double There is the groove that opening portion and depth are less than the thickness of electrode at pole plate side surface；And there is opening portion at barrier film side surface And depth is less than the groove of the thickness of electrode.
When by the plane on the surface parallel to electrode of recess, i.e., the plane definition vertical with the thickness direction of electrode is horizontal stroke During section, the encirclement diameter of a circle of each recess in some cross section can preferably greater than form the hole of the porous body of electrode Average diameter.The average diameter in the hole of porous body is obtained by mercury injection method.
RF batteries have passage at bipolar plates and in the bipolar plates side surface of electrode and barrier film side surface at least Multiple recesses of opening at one.Compared with the region outside the recess of electrode, the recess includes the composition of less electrode Material or the constituent material for being substantially free of electrode.Therefore, recess can have relatively low electrolyte flow resistance, particularly exist Flow resistance on thickness of electrode direction.In RF batteries, even if the size of electrode increases to meet Large Copacity purposes, electrolyte Still it is easy to permeate and spread in the electrodes, causes the good fluidity of electrolyte.Therefore, RF batteries can be reduced by flow resistance The caused pressure loss.
Especially, RF batteries ad-hoc location in the electrodes or the region specifically in the passage in face of bipolar plates There are multiple recesses in (hereinafter sometimes called passage corresponding region).Therefore, with configure the plate electrode without recess situation Compare, the electrolyte in the passage of bipolar plates is easily from the movement of the side of the laterally closer barrier film close to bipolar plates.In RF electricity Chi Zhong, by increasing capacitance it is possible to increase be oriented to the amount of the electrolyte close to barrier film side.In addition, the electrolyte of suction recess is from the inwall for defining recess Permeate and be diffused into the periphery of recess, therefore the diffusion resistance of electrolyte is low.In RF batteries, due to close even in operating current Diffusion resistance is still low during degree increase, so internal resistance can be reduced, therefore can reduce the battery electricity as caused by internal resistance The variable quantity of pressure.
In addition, electrolyte by the periphery of ample supply to recess to carry out cell reaction well.Therefore, in RF batteries In, from close to bipolar plates side to the electrode zone in the recess periphery of barrier film side as cell reaction field, and energy Enough substantially ensure that cell reaction region.Therefore, the RF batteries are utilized, by increasing capacitance it is possible to increase the magnitude of current and height output work(can be obtained Rate.
(2) example of RF batteries can be that scheme is implemented as follows：The recess in the region of passage of electrode The gross area of opening portion is more than the gross area of the recess in the region in addition to the region in face of passage.
If setting recess in the region in addition to passage corresponding region of electrode, diffusion electricity can be further reduced Resistance.Even if when working current density increase, the variable quantity of cell voltage also further can be easily reduced.If on the contrary, Recess is set only in the passage corresponding region of electrode and is substantially not provided with the region outside passage corresponding region recessed Portion, then it can substantially ensure that cell reaction region and reduce the flow resistance and diffusion resistance of electrolyte simultaneously, thus, it is possible to increase Power up flow.
(3) example of RF batteries can be the embodiment that recess includes through hole.
In this embodiment, electrode includes through hole, therefore can further reduce the diffusion resistance of electrolyte.Even if work as During working current density increase, it still is able to further easily reduce the variable quantity of cell voltage.In addition, in the embodiment In, flow resistance of the electrolyte on thickness of electrode direction can be further reduced, and can be substantially ensured that on the periphery of through hole Cell reaction field.In addition, through hole is more easily formed than groove, therefore easy to manufacture has the electrode of through hole.Therefore, the implementation Scheme also has good productivity ratio.
(4) example of RF batteries can be the embodiment that the respective opening diameter of recess is 0.1mm~2.0mm.It is described Opening diameter is the encirclement diameter of a circle of each recess.
In this embodiment, there is provided there is the recess of sufficiently large opening portion, therefore can further reduce electrolyte Diffusion resistance.Even if when working current density increase, the variable quantity of cell voltage also further can be easily reduced.This Outside, in this embodiment, due to providing the recess with sufficiently large opening portion, so opening portion will not be excessive while energy It is enough further to reduce the flow resistance of electrolyte, therefore cell reaction region can be substantially ensured that.
(5) example of RF batteries can be that scheme is implemented as follows：Passage includes：Introduction passage, pass through the introduction passage Electrolyte is fed to electrode；And passing away, the passing away do not connected with introduction passage and independently of introduction passage simultaneously Electrolyte is discharged from electrode by it；And the introduction passage and the passing away each have the area in comb teeth shape Domain, the respective broach of the comb teeth shape are configured in a manner of facing with each other and be interlaced.
The broach of introduction passage and the broach of passing away by it is facing with each other and it is parallel to each other it is interlaced in a manner of configure, And the cell reaction region of electrode is configured in a manner of the broach across configured in parallel.Flow through and configured across broach The amount of the electrolyte in cell reaction region is easier to increase in the case of than introduction passage with passing away not interlocking.Therefore, exist In the embodiment, it can be anticipated that, the cell reaction in the cell reaction region of electrode is activated, and even if works as operating current Also the variable quantity of cell voltage can be reduced during density increase.In addition, in this embodiment, in the cell reaction region of electrode The flow regime of electrolyte be easier to become uniform in whole electrode, and be easy to equably carry in the wide scope of electrode For cell reaction.
(6) example of RF batteries can be that the constituent material of electrode includes the embodiment party of carbon fiber and adhesive carbon Case.
Electrode is suitable as promoting in electrolyte made of conductive carbon material such as carbon fiber and adhesive carbon Active material electrochemical reaction component.In addition, electrolyte is readily permeable into the electrode comprising carbon fiber, therefore it is electrolysed Active material in liquid can carry out cell reaction in cell reaction region well.In addition, include the electrode of adhesive carbon Electric conductivity can be increased and increase intensity.It should be noted that adhesive carbon may cause the flow resistance and diffusion resistance of electrolyte Increase.However, in this embodiment, due to bipolar plates with passage and electrode in passage corresponding region with multiple recessed Portion, so the flow resistance and diffusion resistance of electrolyte also can be easily reduced in the electrode comprising adhesive carbon, And cell reaction region can be substantially ensured that.Therefore, in this embodiment, when working current density increase, also can Enough reduce the variable quantity of cell voltage.
[detailed description of embodiment of the present invention]
Hereinafter, below with reference to the accompanying drawings the redox flow batteries (RF batteries) of embodiment of the present invention are carried out in detail Explanation.In the accompanying drawings, identical reference symbol represents the component with same names.
[embodiment 1]
Said with reference first to essential structures of the Fig. 4 and Fig. 5 to the RF battery systems of the RF batteries 1 comprising embodiment 1 It is bright, then referring to Fig. 1~3 prescribed electrode 10 and bipolar plates 12 in more detail.In Fig. 4, in positive pole groove 106 and negative pole groove 107 Ion be ionic species contained in positive pole and electrolyte liquid example.In addition, in Fig. 4, solid arrow represents charging, And dotted arrow represents electric discharge.
(general introduction of RF batteries)
The RF batteries 1 of embodiment 1 are used as being provided with the RF battery systems of cycling mechanism, the cycling mechanism is to such as figure The circulation-supplied electrolyte of RF batteries 1 shown in 4.Typically, RF batteries 1 pass through AC/DC converter (AC/DC converters) 200 and potential device 210 be connected to generator unit 300 and load 400 such as power system or users.RF batteries 1 are by using hair Electric unit 300 is charged as supply of electric power source, and is discharged by using load 400 as supply of electric power target. The example of generator unit 300 includes solar energy power generating equipment, wind power plant and other general power plants.
(essential structure of RF batteries)
RF batteries 1 have the battery unit 100 as main member, and the battery unit 100 includes：It is supplied positive pole electricity Solve the positive pole 10c of liquid；It is supplied the negative pole 10a of electrolyte liquid；And be arranged on the positive pole 10c and the negative pole 10a it Between barrier film 11.RF batteries 1 include multiple battery units 100, and bipolar plates 12 are included between adjacent battery unit 100 (Fig. 5).
The active material ion that electrode 10 is included in the electrolyte of supply carries out the reacting field of cell reaction.Electrode 10 Porous body therein is flowed through by permission electrolyte to be formed.
Barrier film 11 is by positive pole 10c and negative pole the 10a partition member being spaced apart and is also through predetermined by it The component of ion.
Bipolar plates 12 are provided between positive pole 10c and negative pole 10a and by electric current but not by the conductions of electrolyte Component.
As shown in figure 5, electrode 10 and bipolar plates 12 are tabular components.Bipolar plates 12 are generally made in the form of frame assembly 15 With the frame assembly 15 includes the framing component 150 formed on the periphery of bipolar plates 12.Framing component 150, which has, to be used for By the liquid supply orifice 152c and 152a of electrode 10 that electrolyte is fed in bipolar plates 12 and liquid for discharging electrolyte Body tap 154c and 154a.Framing component 150 is made up of resin with high electrolyte resistance and electrical insulating property etc..
Multiple battery units 100 are stacked and used in the form of being referred to as battery pile.As shown in figure 5, by by frame set The bipolar plates 12 of part 15, positive pole 10c, barrier film 11, negative pole 10a, the bipolar plates 12 etc. of another frame assembly 15 are with the order Repeatedly stacking is carried out to form battery pile.In the case where RF batteries 1 designed to be used Large Copacity purposes etc., prepare comprising pre- The sub- battery pile of the battery unit 100 of fixed number amount, and more sub- battery piles are stacked for using.
Fig. 5 shows the example for providing more sub- battery piles.Collector plate (not shown) is configured in electricity instead of bipolar plates 12 On pole 10, the electrode 10 is located at the both ends on the stacking direction of sub- battery pile or the battery unit 100 in battery pile.End plate 170 are typically configured in the both ends of the stacking direction of the battery unit 100 in battery pile, and a pair of end plate 170 and such as long spiral shell The engagement member 172 of bolt engages and integration.
(cycling mechanism)
Cycling mechanism includes：Positive pole groove 106, the positive pole groove 106 store circulation-supplied to positive pole 10c anolyte Liquid；Negative pole groove 107, the negative pole groove 107 store circulation-supplied to negative pole 10a electrolyte liquid；Connect positive pole groove 106 and RF The pipeline 108 and 110 of battery 1；Connect the pipeline 109 and 111 of negative pole groove 107 and RF batteries 1；And it is separately positioned on upstream side Pump 112 and 113 on (supply side) pipeline 108 and 109.By stack multiple frame assemblies 15, liquid supply orifice 152c and 152a and liquid discharge orifice 154c and 154a form electrolyte flow pipeline, and pipeline 108~111 is connected to the pipe Line.
(general introduction of RF battery systems)
In RF battery systems, circulated by using the anode electrolyte comprising positive pole groove 106 and pipeline 108 and 110 logical Road and the electrolyte liquid circulation canal comprising negative pole groove 107 Yu pipeline 109 and 111, anode electrolyte circulation-supplied is arrived Positive pole 10c, and by electrolyte liquid circulation-supplied to negative pole 10a.As the result of circulation-supplied, RF batteries 1 are in response to conduct The chemical valence reacting condition of the ion of active material in the electrolyte of each electrode and carry out discharge and recharge.RF battery systems it is basic Known construction can be suitably used in construction.
(bipolar plates and electrode)
The feature of the RF batteries 1 of embodiment 1 is for example as follows：Bipolar plates 12 have on its surface in face of electrode 10 Passage 120, electrolyte flow through the passage 120 (Fig. 1)；And electrode 10 is in the position overlapping with the passage 120 of bipolar plates 12 Place has multiple recess 10h, and the electrolyte in passage 120 is directed to close to the side of barrier film 11 (figure by the recess 10h 3).In fig. 1 and 2, in order to it is more readily appreciated that bipolar plates 12 are shown as into thicker in an exaggerated manner.
Bipolar plates
Bipolar plates 12 are provided between adjacent battery unit 100 (Fig. 5) and are used as anode electrolyte and negative electricity Solve the conductive member of the dividing plate between liquid.Bipolar plates 12 are typically the flat board with rectangular shape as shown in Figures 2 and 3.It is double Pole plate 12 is arranged between positive pole 10c and negative pole 10a so that the preceding surface and rear surface of bipolar plates 12 face adjacent electricity respectively The positive pole 10c of a battery unit 100 in the pool unit 100 and negative pole 10a of another battery unit 100.Bipolar plates 12 First surface (preceding surface) is the surface for facing positive pole 10c, and its second surface (rear surface) is in face of negative pole 10a surface.
Passage
Bipolar plates 12 have groove opening on its surface in face of electrode 10.Groove is used as the passage that electrolyte flows through 120.Set passage 120 with each battery unit 100 by pump 112 and 113 (Fig. 4) to flowing to the electrolyte of electrode 10 Flowing is adjusted.Fig. 1 is shown wherein has passage 120 at each surface of the bipolar plates 12 in its preceding surface and rear surface Example.Anode electrolyte, which flows through, is arranged on leading at the first surface of the bipolar plates 12 configured in a manner of in face of positive pole 10c Road 120.Electrolyte liquid stream crosses the passage being arranged at the second surface of the bipolar plates 12 configured in a manner of in face of negative pole 10a 120.It is used as the shape and size of the groove of passage 120 by regulation, electrolyte in each battery unit 100 can be adjusted Flowing.
Shape
As shown in Figures 2 and 3, the passage 120 in the example includes for electrolyte being fed to the He of introduction passage 122 of electrode 10 The passing away 124 that electrolyte is discharged from electrode 10.Introduction passage 122 and passing away 124 do not communicate with each other simultaneously mutually solely It is vertical.Introduction passage 122 and passing away 124 each have the region in comb teeth shape.Passage 120 has the comb for facing and interlocking Odontoid, the wherein broach of the broach of introduction passage 122 and passing away 124 are matched somebody with somebody in a manner of facing with each other and be interlaced Put.
Introduction passage 122 includes：Introducing portion 122i, the introducing portion 122i are connected to liquid supply orifice 152c or 152a (Fig. 5) and it is supplied electrolyte；Lateral trench portion 122x, the lateral trench portion 122x are connected to the introducing portion 122i simultaneously Extend on the horizontal direction (left and right directions in Fig. 3) of bipolar plates 12；And multiple longitudinal groove portion 122y, it is the multiple vertical Extend to groove 122y from the lateral trench portion 122x on the longitudinal direction of bipolar plates 12 (in Fig. 3, above-below direction) And C is configured (Fig. 3) in parallel relationship at a predetermined interval.Introducing portion 122i, lateral trench portion 122x and longitudinal groove Portion 122y is continuous.
Passing away 124 has the shape similar to introduction passage 122.Passing away 124 includes：Discharge unit 124o, institute Discharge unit 124o is stated to be connected to liquid discharge orifice 154c or 154a (Fig. 5) and electrolyte is flowed through into electrode from introduction passage 122 10 grades and discharge；Lateral trench portion 124x, the lateral trench portion 124x are connected to discharge unit 124o and in the horizontal strokes of bipolar plates 12 Upwardly extended to side；And multiple longitudinal groove portion 124y, the multiple longitudinal groove portion 124y is from lateral trench portion 124x Extend on the longitudinal direction of bipolar plates 12 and C is configured in parallel relationship at a predetermined interval.Discharge unit 124o, transverse direction Groove 124x and longitudinal groove portion 124y is continuous.
The longitudinal groove portion 124y of passing away 124 is configured between the adjacent longitudinal groove portion 122y of introduction passage 122. That is, introduction passage 122 longitudinal groove portion 122y and passing away 124 longitudinal groove portion 124y in a lateral direction It is alternately arranged.Using this construction, the electrolyte formation supplied from introducing portion 122i is such as the arrow of left and right directions in Fig. 3 and up and down The flowing of the shape along passage 120 shown in the arrow in direction, and formed as shown in the arrow of the incline direction in Fig. 3 Pass through horizontal direction of the spine 126 between longitudinal groove portion 122y and 124y between longitudinal groove portion 122y and 124y On flowing.Introduced from introducing portion 122i and flow through passage 120 to discharge unit 124o electrolyte with face of bipolar plates 12 Permeate and spread in the electrode 10 that mode configures.Power supply 122i of the electrolyte for permeating and spreading in electrode 10 from electrode 10 Effluent is to discharge unit 124o sides and cell reaction is carried out in electrode 10 simultaneously.Especially, in this example, due to electrode 10 Constituent material is fully present in the region of the electrode 10 configured in a manner of the spine 126 in face of bipolar plates 12, so electric Solution liquid is maintained in electrode 10, and cell reaction is carried out well.As noted previously, as electrolyte is being indulged by electrode 10 Flowed in a lateral direction between groove 122y and 124y, so can reduce with the electrolyte of unreacted state discharge Amount.Therefore, it is possible to improve the magnitude of current of RF batteries 1, therefore working current density can be improved.In addition, by increasing capacitance it is possible to increase the magnitude of current RF batteries be properly termed as reducing the RF batteries of internal resistance.
In this example, in this example lateral trench portion 122x and 124x and longitudinal groove portion 122y's and 124y Opening portion has the rectilinear form for combining multiple rectangles as shown in Figure 3, and has rectangular cross-sectional shape as shown in Figure 1.
Whole passage 120 has uniform depth D in this example12(Fig. 1).The lateral trench portion of introduction passage 122 122x length Lx is equal to the lateral trench portion 124x of passing away 124 length Lx, the longitudinal groove portion of introduction passage 122 122y width Wy is equal to the longitudinal groove portion 124y of passing away 124 width Wy, and the longitudinal groove portion of introducing portion 122 122y length Ly is equal to the longitudinal groove portion 124y of passing away 124 length Ly.The longitudinal groove portion 122y of introducing portion 122 Between interval C be equal to passing away 124 longitudinal groove portion 124y between interval C.Preferably, passage 120 is formed Groove has substantially the same shape and the size being substantially equal, because electrolyte can be in whole bipolar plates 12 and with face Equably flowed in the whole region of the electrode 10 configured to the mode of the bipolar plates 12.
Introducing portion 122i and discharge unit 124o in the example configure the horizontal direction in lateral trench portion 122x and 124x On end and rectangular bipolar plate 12 diagonal position.Therefore, electrolyte is easily produced in the longitudinal and lateral directions to exist Flowing in bipolar plates 12 and flowing of the electrolyte of electrode 10 in electrode 10 is fed to by passage 120.It will can be electrolysed Liquid is sufficiently remained in electrode 10, therefore can carry out cell reaction well.
In addition, as the example shown in Fig. 1, groove is all set at the preceding surface of bipolar plates 12 and rear surface Liang Ge surfaces In the case of, it is preferred that in the perspective view of bipolar plates 12, at least a portion of the groove at preceding surface with rear At least a portion of groove at surface is overlapping, because the flowing of anode electrolyte and the flowing of electrolyte liquid can be uniform. In this example, in the perspective view of bipolar plates 12, lateral trench portion 122x and 124x at the preceding surface of bipolar plates 12 And lateral trench portion 122x at longitudinal groove portion 122y and 124y and its back side and 124x and longitudinal groove portion 122y and 124y is overlapping.
Specific size
The specific size of Primary Reference Fig. 1 and the passage of 3 pairs of bipolar plates 12 120 illustrates.It is each shown in Fig. 1-Fig. 3 The size and number of individual component are only examples and can suitably changed.
Form the depth D of the groove of passage 12012For example, the 10%~45% of the thickness of bipolar plates 12.Such as this example, In the perspective view of bipolar plates 12, groove at the preceding surface of bipolar plates 12 feelings overlapping with the groove thereafter at surface Under condition, if the thickness D of groove12Excessive, then mechanical strength may reduce.Therefore, the depth D of groove12Preferably bipolar plates 12 Thickness 10%~35%.
As the cross-sectional area for the groove for forming passage 120 is bigger, the flow resistance drop of the electrolyte in battery unit 100 It is low, and it can be anticipated that the reduction of the pressure loss.It is therefore preferable that according to above-mentioned depth D12To select the opening portion of each groove Width Wy etc. so that cross-sectional area is sufficiently large.For example, be configured with the longitudinal groove portion 122y and 124y of electrode 10 opening portion Width Wy is preferably 0.1mm~2.0mm.The width Wy of opening portion can be 0.1mm~1.3mm, 0.1mm~1mm, 0.1mm~ 0.8mm or 0.1mm~0.5mm.
Constituent material
The constituent material of bipolar plates 12, which can be used suitably, not to react with electrolyte and has electrolyte resistance (chemically-resistant Property, acid resistance etc.) low resistance conductive material.In addition, the constituent material of bipolar plates 12 preferably has appropriate rigidity.This be because It will not almost change for a long time to form the shape and size of the groove of passage 120, and can easily keep being obtained by passage 120 The effect of the reduction flow resistance obtained and the effect for reducing the pressure loss.Specific constituent material can contain carbon material and organic The composite of material, more specifically containing conducting inorganic material such as graphite and organic material such as TPO organic compound Or the Markite of chloridized organic compounds.
Carbon material can be such as graphite and carbon black or diamond-like-carbon (DLC).Carbon black can be acetylene black or stove It is black.Carbon material preferably comprises graphite.Carbon material can mainly include graphite, and partly can include in carbon black and DLC It is at least one.In addition to carbon material, conducting inorganic material can also include the metal of such as aluminium.Conducting inorganic material can be Powder or fiber.
TPO organic compound can be polyethylene, polypropylene or polybutene.Chloridized organic compounds can be chlorine Ethene, haloflex or chlorinated paraffin.
Bipolar plates 12 with passage 120 can by being such as injection moulded, compressing or vacuum forming known formula Above-mentioned constituent material is configured to tabular by method, and is used as by being formed the groove of passage 120 to manufacture.If groove with it is bipolar Plate 12 is formed simultaneously, then bipolar plates 12 have good productivity ratio.The groove of passage 120 can be by cutting without passage 120 Sheet material and formed.
Electrode
Electrode 10 is arranged between barrier film 11 and bipolar plates 12.Mainly electrolyte is supplied by the passage 120 of bipolar plates 12 Electrode 10 should be arrived.Electrolyte permeates and spread in electrode 10, and it is anti-that the active material in electrolyte carries out battery in electrode 10 Should, and reacted electrolyte is discharged from electrode 10.Because the purpose, electrode 10 is by the porous body with multiple pores It is made.Electrode 10 is typically rectangular flat as shown in Figures 2 and 3.
The first surface of electrode 10 is the barrier film side surface configured in a manner of in face of barrier film 11.The second surface of electrode 10 It is the bipolar plates side surface configured in a manner of in face of bipolar plates 12.In this example, as shown in Figure 3, electrode 10 is configured to Covering be included in bipolar plates 12 in face of the surface of electrode 10 at formed passage 120 in formation longitudinal groove portion 122y and 124y region.Fig. 3 shows arrangement of the electrode 10 in bipolar plates 12 so that in two ends of the longitudinal direction of electrode 10 Edge (top edge and lower edge) is overlapping with lateral trench portion 122x and 124x.In this case, the horizontal direction of electrode 10 On length be substantially equal to length on the horizontal direction of bipolar plates 12.Length on the longitudinal direction of electrode 10 is slightly less than bipolar Length on the longitudinal direction of plate 12, and the lateral trench portion 122x slightly larger than introduction passage 122 and passing away 124 horizontal stroke To the distance between groove 124x.
Recess
Electrode 10 has multiple recess 10h at it in the region (passage corresponding region) of the passage 120 of bipolar plates 12. In electrode 10 as shown in Figure 3 from the plan of barrier film side, passage corresponding region in this example is and passage 120 Multiple rectangular areas overlapping with 124y longitudinal groove portion 122y.In this example, each rectangular area has multiple recesses 10h。
Recess 10h is by the electrolyte in passage 120 from the side of the close bipolar plates 12 of electrode 10 (side of bipolar plates 12) court Electrode 10 is directed to the side (side of barrier film 11) of the close barrier film 11 of electrode 10.Recess 10h shown in Fig. 1~3 is respectively Extend to the through hole in face of the surface of barrier film 11 (barrier film side surface) of electrode 10 from the bipolar plates side surface of electrode 10, and All it is opening at bipolar plates side surface and the surface of barrier film side surface two.Because recess 10h is from the bipolar plates side surface of electrode 10 Barrier film side surface is extended to, so the electrolyte in the passage 120 of bipolar plates 12 can be as illustrated by the arrows in fig. 1 by fully Barrier film side surface is directed to from bipolar plates side surface.It is moved in electrolyte by recess 10h from the side of bipolar plates 12 of electrode 10 While 11 side of barrier film, electrolyte oozes via the hole of the opening at the inwall for defining recess 10h in recess 10h neighboring area Thoroughly and spread.The electrolyte spread in recess 10h neighboring area rests on the position and to carry out battery anti-with a certain amount of Should.Because electrode 10 as described above has recess 10h, so constituent material of the electrode 10 at recess 10h parts is reduced, in addition In this example, electrode 10 at recess 10h parts essentially without constituent material.Therefore, electrolyte is easily in electrode 10 Permeate and spread from the lateral side of barrier film 11 of bipolar plates 12 on thickness direction.Therefore, it is possible to reduce flow resistance and diffusion resistance, and In the example that recess 10h is through hole, resistance can be further reduced.Cell reaction is carried out in addition, can substantially ensure that Region, and the utilization ratio of electrode 10 can be improved.
Shape
Each recess 10h shape can be selected suitably.Fig. 1~3 show the example that recess 10h is cylinder-shaped hole. In the example, recess 10h opening portion is circular (Fig. 2 and 3), and recess 10h cross section is rectangular (Fig. 1).If recess 10h is the through hole for having on depth direction as described above homogeneous shape and single-size, then can easily form recess 10h And therefore electrode 10 has good productivity ratio.Or recess 10h opening portion can be in non-circular shape, such as rectangle Shape or elliptical shape.
The method for forming recess
The recess 10h formed by through hole can be formed by using the drilling instrument of such as puncher or laser.
Specific size
It is assumed that the size (opening diameter R) of recess 10h opening portion is sufficiently above the pore for the porous body for forming electrode 10 Average diameter.Specifically, the size (opening diameter R) of recess 10h opening portion is preferably 10 times of the average diameter in hole More than, more preferably more than 30 times.Recess 10h can separate according to size and porose area.If in addition, use above-mentioned cutting element To form recess 10h, then it can retain cut mark.According to the presence of cut mark, recess 10h and porose area can be separated.
The encirclement circle of recess 10h opening portion is defined, and encirclement diameter of a circle is assumed to recess 10h opening diameter R. For example, as the opening diameter R of the recess 10h at bipolar plates side surface is bigger, electrolyte is easier by leading to from bipolar plates 12 The inside in road 120 is directed to the side of barrier film 11 of bipolar plates 12.It can be anticipated that the flow resistance of electrolyte and the reduction of diffusion resistance. Or for example, as the opening diameter R of the recess 10h at barrier film side surface is bigger, electrolyte is easier in the close of electrode 10 The regional diffusion of barrier film 11, and cell reaction is easier close to the progress of the region of barrier film 11.In these viewpoints, for example, opening Mouth diameter R can be substantially equal to longitudinal groove portion 122y and 124y width Wy.On the contrary, the opening diameter R with recess 10h It is smaller, caused by recess 10h the reduction of the mechanical strength of electrode 10 more easily diminish.If opening diameter R is small, can It is enough to reduce the flow resistance of electrolyte and diffusion resistance by increasing recess 10h quantity.
If recess 10h's is oversized, or if recess 10h quantity is excessive, then may reduce electrode 10 Cell reaction region, and reaction resistance may be improved, or the intensity of electrode 10 may reduce.In these viewpoints, open Mouth diameter R can be longitudinal groove portion 122y and 124y width Wy more than 5%, the 10%~100% of width Wy or width The 50%~80% of Wy.Recess 10h specific opening diameter R for example can be 0.1mm~2.0mm, 0.1mm~1.3mm, 0.5mm~1.2mm or 0.8mm~1.0mm.Except the passage of bipolar plates 12 configured in a manner of in face of corresponding recess 10h Outside 120 size (particularly in this example, longitudinal groove portion 122y and 124y width Wy and length Ly), recess 10h Opening portion size can contemplate recess 10h quantity, the quantity in cell reaction region in addition to recess 10h and Mechanical strength of electrode 10 etc. selects.
Existence
Recess 10h can be present in the passage corresponding region of electrode 10 as shown in Figures 2 and 3, and can be not present in In region in addition to passage corresponding region.In this embodiment, it is present in recessed in the region outside passage corresponding region The gross area Sr of the opening portion in portion relative to the opening portion for the recess 10 being present in the passage corresponding region of electrode 10 total face Product S10hPercentage ((Sr/S10h) × 100) it is 0%.Therefore, gross area S10hIt is more sufficiently large than gross area Sr.In the embodiment In, electrolyte permeates and spread in the region outside the passage corresponding region of electrode 10, or mainly with face of bipolar plates Permeate and spread in the region that the mode of 12 spine 126 (Fig. 1) configures, the region can be appropriately as active material Reacting field, and reacting field can be substantially ensured that.In addition, in this embodiment, it can reduce caused by recess 10h The reduction of the mechanical strength of electrode 10, and intensity is high.
It is assumed that the gross area S of the opening portion of recess 1010hRelative in the passage 120 of bipolar plates 12 covered with electrode 10 Part opening portion gross area S120The percentage of (in this example, the longitudinal groove portion 122y and 124y gross area), i.e., (S10h/S120) × 100 are used as accounting.As accounting is bigger, the electrolyte in passage 120 can be more by the recess of electrode 10 10h is guided.As accounting is smaller, the cell reaction region on recess 10h periphery can be substantially ensured that.Consider electrolyte to recess 10h supply and the holding in the cell reaction region in recess 10h periphery, the accounting is preferably from about 10%~about 90%, even more preferably about 30%~about 90%, or be also preferably about 50%~about 80%.
Constituent material
The constituent material of electrode 10 can preferably use the porous body such as carbon felt or carbon paper of carbon fiber-containing.Except carbon fiber it Outside, the constituent material of electrode 10 can use the porous body for including adhesive carbon.Adhesive carbon is used for the electric conductivity for increasing carbon felt, And for increasing the intensity of carbon paper.In the case of the porous body comprising adhesive carbon, adhesive carbon can increase electrolyte Flow resistance and diffusion resistance, and mobility may be caused to reduce.However, because electrode 10 has recess 10h, so recessed Portion 10 can reduce the flow resistance and diffusion resistance of electrolyte.
Carbon felt or carbon paper can use known or commercially available.Recess 10h can be closed by using as described above Suitable instrument is formed in commercially available carbon felt or carbon paper.If using carbon felt, it can be anticipated that favourable effect is to cause：(1) inciting somebody to action The aqueous solution is used to still be difficult to generation oxygen in the case where producing the current potential of oxygen when charging in the case of electrolyte；(2) it is electrolysed Liquid has good mobility.If using carbon paper, it can be anticipated that the beneficial effect of (1) high conductivity and (2) high intensity.
(other components)
Electrolyte
The electrolyte used in RF batteries 1 includes active material ion, such as metal ion and nonmetallic ion.Electrolysis The example of liquid includes vanadium (V) ion (Fig. 4) comprising different valence state as positive active material and the vanadium base of negative electrode active material Electrolyte.The example of other electrolyte includes comprising iron (Fe) ion as positive active material and includes chromium (Cr) ion conduct Iron-chromium electrolyte of negative electrode active material and as positive active material and include titanium (Ti) ion conduct comprising manganese (Mn) ion The manganese of negative electrode active material-titanium electrolyte.As electrolyte, can use also included in addition to the active material be selected from by The aqueous solution of at least one of group that sulfuric acid, phosphoric acid, nitric acid and hydrochloric acid are formed acid or acid salt.
Barrier film
As barrier film 11, such as amberplex such as cation-exchange membrane or anion-exchange membrane can be used.Ion is handed over Changing film has such as following feature：(1) between the ion of positive active material and the ion of negative electrode active material it is good every From；(2) H as the electric charge carrier in battery unit 100+The good permeability of ion, and can be suitable for every Film 11.As barrier film 11, known barrier film can be used.
(main beneficial effect)
In the RF batteries 1 of embodiment 1, bipolar plates 12 have passage 120, and electrode 10 has with face of passage Multiple recess 10h in the passage corresponding region that 120 mode configures.Therefore, in RF batteries 1, the electrolyte in passage 120 The side of barrier film 11 can be directed to from the side of bipolar plates 12, electrolyte permeates and spread on recess 10h periphery during guiding, and Cell reaction can be carried out on recess 10h periphery.That is, in RF batteries 1, the diffusion electricity of electrode 10 can be reduced Resistance, and even if when working current density increase, can also reduce the variable quantity of cell voltage.Will be in following test examples 1 The beneficial effect is specifically described.
In addition, in RF batteries 1, because bipolar plates 12 have a passage 120, and electrode 10 have in ad-hoc location it is multiple recessed Portion 10h, so the flow resistance on the thickness direction of electrode 10 can be reduced, cause good mobility, in recess 10h week While being able to ensure that the reacting field for cell reaction, and further it is able to ensure that the reaction from the side of bipolar plates 12 to the side of barrier film 11 .Therefore, the magnitude of current in RF batteries 1 increases and can obtain high power output.Such RF batteries 1 can be suitable for Large Copacity purposes.
[test example 1]
For the wherein bipolar plates as described in embodiment 1 with passage and electrode in passage corresponding region with The RF batteries of multiple recesses, the polarization characteristic examination of cell voltage when carrying out applying electric current under various current densities for measuring Test, and have evaluated the performance of RF batteries.
In this experiment, the RF batteries of three types are prepared for, the three types include：Sample 1-1 (has ditch Groove, with hole), wherein bipolar plates with passage (groove) and electrode in ad-hoc location with multiple recesses (hole)；Sample 1-100 Number (no groove, non-porous), wherein bipolar plates do not have passage, and electrode does not have recess, and both are flat board；And sample No. 1-200 (having groove, non-porous), wherein bipolar plates have passage, and electrode without recess and is flat board.Table I lists examination Test the specification of the middle RF batteries used.
The respective material of bipolar plates, electrode and barrier film is all identical for any sample.In addition, each sample is all Monocell.
For No. 1-1 electrode used of sample, the carbon felt in Table I is prepared, and by using drilling instrument etc., only vertical The through hole for the opening diameter R (mm) for by the quantity in Table I being prepared for having into groove in Table I.
Sample 1-1 and sample 1-200 uses have the electrode of identical size, and are hindered in view of the flowing of electrolyte Power, sample 1-100 uses are than for No. 1-1 electrode small with the electrode of No. 1-200 of sample.
In this experiment, the vanadium base electrolyte for being prepared for each using the charged state (SOC) in Table I to be 50% is as electricity Solve the sample (RF batteries) of liquid.The flow flow of the electrolyte of each sample being adjusted in Table I so that the stream of per unit area It is equal to each other in quality entity.Then the initial cell voltage E when applying electric current under each current density is measured0(V) and stably Cell voltage E (V).Fig. 6 shows result.
Initial cell voltage E0It is to measure cell voltage in order when applying the electric current of steady state value current density and obtain And be when mainly due to the conductive resistance included in the internal resistance of RF batteries and reaction resistance quick voltage occurring The cell voltage obtained during decline.
Stable cell voltage E is when mainly due to the internal resistance included in RF batteries after above-mentioned quick voltage declines In diffusion resistance and occur that medium voltate declines, voltage declines the battery electricity for substantially stopping and obtaining during voltage stabilization Pressure.
In addition, obtain initial cell voltage E0With the difference (E between stable cell voltage E0-E)(V).Fig. 7, which is shown, to be finished Fruit.Voltage difference (E-E0) (V) be considered as the overvoltage based on diffusion resistance.In this case, potential difference is referred to as concentration mistake Voltage.
In addition, it is 0.05A/cm to obtain current density2When total battery resistivity (Ω cm2) and diffusion resistance composition Resistivity (Ω cm2).Table I shows result.Current value by using stable cell voltage E and now obtains total electricity Pond resistivity.Current value by using above-mentioned voltage difference (concentration overvoltage) and now, obtain the resistance of diffusion resistance composition Rate (diffusion resistance rate).
[Table I]
In figure 6, transverse axis represents current density (A/cm2) and longitudinal axis expression cell voltage (V).Dotted line represents each sample Initial cell voltage E0, and solid line represents the stable cell voltage E of each sample.From Fig. 6 curve map, it can be seen that with The increase of current density, initial cell voltage E0Both reduce with stable cell voltage E.Especially find, by current density Stable cell voltage E decrement caused by increase is more than the initial voltage E as caused by increasing current density0Decrement.
In addition, from Fig. 6 curve map, it can be seen that the initial cell voltage E of each sample0Substantially it is equal to each other and not Tangible difference.On this, alternatively it is conceivable to, may due to the reaction resistance of the original conductive resistance of electrode and cell reaction Voltage can occur in the initial power-up stage to decline, and the presence or absence of recess in the presence or absence of passage in bipolar plates and electrode Influence small.
On the contrary, the decrement d of the stable cell voltage E as caused by increasing current densityEChange with sample.
Relatively small decrement d is provided in the case of without groove and non-porous sample 1-100E.Because In the case of sample 1-100, as shown in Table I, total battery resistivity is relatively small and diffusion resistance rate is also relatively small.By It is small in total battery resistivity and diffusion resistance rate, so in the case of sample 1-100, as shown in fig. 7, being increased by current density The incrementss of above-mentioned voltage difference (concentration overvoltage) are relatively small caused by adding.Thus, in the case of sample 1-100, electricity Solution liquid is easy to permeate and spread in the electrodes, and fully carries out cell reaction.However, in the case of sample 1-100, due to Electrode size increase causes flow resistance increase and pressure loss increase, so electrode size can not increase, therefore sample 1-100 Number Large Copacity purposes is not suitable for.In this experiment, the size of the electrode of sample 1-100 be sufficiently smaller than sample 1-1 and The size of the electrode of No. 1-200.
In the case of with groove and non-porous sample 1-200, flowing can be reduced by the passage of bipolar plates Resistance；However, as shown in Fig. 6 curve map, the stable cell voltage E decrement d as caused by increasing current densityEGreatly.This It is because as shown in Table I, in the case of sample 1-200, total battery resistivity is big and diffusion resistance rate is also big.Due to Total battery resistivity and diffusion resistance rate are big, so in the case of sample 1-200, it is above-mentioned as caused by increasing current density The increment of voltage difference (concentration overvoltage) is big, as shown in Figure 7.In this experiment, such as when current density is about 0.45A/cm2 When, the concentration overvoltage that sample 1-200 is more than 2 times of the concentration overvoltage of sample No. 1-1 and No. 1-100.On this Point, the reduction that passage is not sufficient enough to reduce the cell voltage as caused by increasing current density is provided only in bipolar plates.
In the case of with groove and the sample in hole 1-1, as shown in Fig. 6 curve map, drawn by current density increase The stable cell voltage E risen reduction amount dEIt is minimum in three samples.Because as shown in Table I, sample 1-1 it is total Battery resistivity and diffusion resistance rate are less than sample 1-100, therefore can fully reduce internal resistance.Due to total battery electricity Resistance rate and diffusion resistance rate are sufficiently small, therefore in the case of sample 1-1, the above-mentioned voltage difference as caused by increasing current density The incrementss of (concentration overvoltage) are small and are substantially identical to sample 1-100, as shown in Figure 7.
Above-mentioned result of the test shows, if bipolar plates with passage and electrode in ad-hoc location with multiple recesses, then The variable quantity of cell voltage can also be reduced even if when working current density increase.In this experiment, discharge current density increases Add.However, even if the density of charging current increases, if bipolar plates with passage and electrode in ad-hoc location with multiple recessed Portion, it becomes possible to reduce the variable quantity of cell voltage.
[variation]
Following deform can be carried out to the RF batteries 1 of embodiment 1.
(bipolar plate channels)
(1) bipolar plates 12 only have passage 120 on preceding surface or rear surface, and only with face of with passage 120 The electrode 10 that the mode on surface configures has multiple recess 10h.
(2) in the case where bipolar plates 12 all have passage 120 at both preceding surface and rear surface place, in bipolar plates 12 In perspective view, the passage 120 at preceding surface is not overlapping with the passage 120 at rear surface.
(3) in the case that there is the comb teeth shape for facing and interlocking in passage 120, the broach of introduction passage 122 and discharge The broach of passage 124 extends on horizontal direction (left and right directions in figure 3), and in the longitudinal direction (in Fig. 3 of bipolar plates Above-below direction) on be alternately arranged.
(4) passage 120 have face and the comb teeth shape of noninterlace, wherein introduction passage 122 and passing away 124 each other Do not interlock.For example, the longitudinal groove portion of introduction passage and the longitudinal groove portion of passing away can be in the longitudinal direction sides of bipolar plates 12 It is facing with each other at certain intervals upwards.Under the comb teeth shape of noninterlace, in electrode 10, in face of being arranged on adjacency channel Between the region of electrode 10 that configures of mode of spine worked as cell reaction region, and can reduce with unreacted The amount of the electrolyte of state discharge.
(5) at least one of introduction passage 122 and passing away 124 are not continuous grooves, but are broken including one group Continuous groove.For example, longitudinal groove portion can be included on the longitudinal direction (above-below direction in Fig. 3) of bipolar plates between certain Every one group of groove of configuration.In this case, bipolar plates are not only included in the spine extended on horizontal direction, and are included in The spine extended on longitudinal direction.The region of the electrode configured in face of the mode of these spines can be played as cell reaction area The effect in domain.Cell reaction region, and the increase of prospective current amount can be increased.
(6) introducing portion 122i and discharge unit 124o configures the center on lateral trench portion 122x and 124x horizontal direction Portion.
(7) formed passage 120 groove opening portion shape have it is such as wavy or shape serpentine shape.Respectively The above-mentioned shape of cross section of individual groove is the shape for having curved surface, such as semicircular in shape or the rectangle shape with fillet Shape.In addition, groove can be the width of the bottom dovetail groove bigger than opening diameter.
(8) the depth D of the groove of passage 120 is formed12, width Wy, length Ly and interval at least one of C be part not With.For example, introducing portion 122 and discharge unit 124 can have different depth D12, different width Wy and different length Ly。
(recess of electrode)
(1) the shape and size part on recess 10h depth direction is different.For example, recess 10h can each have The size of conical by its shape, wherein opening portion from the side of bipolar plates 12 of electrode 10 towards the side of barrier film 11 continuously or step by step increase or Reduce.In this case, recess 10h shape of cross section is trapezoidal shape.
(2) recess 10h is hole with the end (closed pore) or the groove for only having in the bipolar plates side surface of electrode 10 opening portion. Or recess 10h is hole with the end (closed pore) or the groove for only having in the barrier film side surface of electrode 10 opening portion.Hole or groove Depth be greater than electrode 10 thickness 50% and less than electrode thickness., can as the depth of hole or groove is bigger The electrolyte increased in the passage 120 of bipolar plates 12 is oriented to the amount of the side of barrier film 11, and can improve the utilization ratio of electrode 10. Therefore, the depth of hole or groove can be preferably the thickness of electrode 10 more than 60%, more than 70%, more than 80% or 90% with On.The constituent material at the groove forming position of electrode material is removed by using the instrument of such as pin or cutter, can To form hole or groove.
(3) electrode 10 includes both through hole and groove as recess 10h.
(4) region of the electrode 10 outside passage corresponding region includes recess 10h.In this case, electrode 10 The gross area S of the opening portion of recess 10 in passage corresponding region10hIt is recessed in region preferably greater than outside passage corresponding region Gross area Sr (the S of the opening portion in portion 1010h>Sr).Therefore, as described above, the reacting field of active material can be substantially ensured that.Examine Considering ensures cell reaction field, above-mentioned percentage (Sr/S10h) × 100 are preferably less than 20%, less than 15% or less than 10%.
In view of ensuring cell reaction field, percentage (Sr/S10h) × 100 are most preferably 0%.If recess 10 is as implemented Scheme 1 is equally existed only in passage corresponding region, then percentage (Sr/S10h) × 100 are 0%.
The invention is not restricted to examples detailed above, but it is defined by the claims, and is intended to include being equal with claims Implication and scope in all modifications.For example, the area of electrode and thickness, the specification (example of recess in test example 1 can be changed Such as size, number and shape), the specification of the passages of bipolar plates (such as the size in longitudinal groove portion and lateral trench portion, shape and Quantity) and electrolyte type.
Industrial applicability
The redox flow batteries of the present invention can be used in battery, and the battery is intended to for generating electricity by natural energy Power output such as solar energy power generating, wind-power electricity generation or other power generation stabilization generation powers changes, when generated energy is excessive Store electric power and balanced load.The redox flow batteries of the present invention can also act as battery, and the battery is intended to When being provided to general power plant as reply voltage dip or the countermeasure and balanced load of power failure.Especially, oxygen of the invention The large-capacity battery that purpose is above-mentioned purpose can be suitable for by changing reduction flow battery.
Label declaration
1：Redox flow batteries (RF batteries)
10：Electrode, 10c：Positive pole, 10a：Negative pole, 10h：Recess
11：Barrier film
12：Bipolar plates
120：Passage, 122：Introduction passage, 124：Passing away, 126：Spine
122i：Introducing portion, 124o：Discharge unit
122x、124x：Lateral trench portion, 122y, 124y：Longitudinal groove portion
100：Battery unit
15：Frame assembly, 150：Framing component
152c、152a：Liquid supply orifice, 154c, 154a：Liquid discharge orifice
170：End plate, 172：Engagement member
106：Positive pole groove, 107：Negative pole groove, 108~111：Pipeline
112、113：Pump
200：AC/DC converter, 210：Potential device, 300：Generator unit, 400：Load

Claims (6)

1. a kind of redox flow batteries, it is included：
Electrode, electrolyte is supplied to the electrode；
Barrier film, the barrier film are configured in a manner of the first surface in face of the electrode；And
Bipolar plates, the bipolar plates are configured in a manner of the second surface in face of the electrode,
Wherein described bipolar plates have passage on its surface in face of the electrode, and the electrolyte flows through the passage, and
Wherein described electrode has multiple recesses in its region in face of the passage, and the recess is by the institute in the passage Electrolyte is stated from the guiding of the side of the laterally closer barrier film close to the bipolar plates.
2. redox flow batteries according to claim 1, wherein,
The gross area in the opening portion of the recess in the region of the passage of the electrode, which is more than, to be removed in face of described The gross area of the recess in region outside the region of passage.
3. redox flow batteries according to claim 1 or 2, wherein,
The recess includes through hole.
4. according to redox flow batteries according to any one of claims 1 to 3, wherein,
The respective opening diameter of recess is 0.1mm~2.0mm.
5. according to redox flow batteries according to any one of claims 1 to 4,
Wherein described passage includes：Introduction passage, the electrolyte is fed to by the electrode by the introduction passage；And row Go out passage, the passing away does not connect with the introduction passage and independently of the introduction passage and by it by the electrolysis Liquid is discharged from the electrode, and
Wherein described introduction passage and the passing away each have a region in comb teeth shape, the comb teeth shape it is respective Broach configured in a manner of facing with each other and be interlaced.
6. according to redox flow batteries according to any one of claims 1 to 5, wherein,
The constituent material of the electrode includes carbon fiber and adhesive carbon.
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